Fungus-proofing composition



Patented July 12 STAT ES G FFI CE FUNGUS -PROOFIN G GOMPQS'LTIGN Paul G'eorge Beni'gnus, Belleville, 111., 'assignor to Monsanto Chemical Company; St;- Iii-mic; Moi, a; corporation: of Delaware No Drawing, ApplicationAugustll 1M4;. SeriaI'No. 549,138

terial's" may be rendered highly and permanently resistant to attack by fungus and bacteria;

When cellulosic materials such" as fabrics are immersed in a bath contaii'ii'ng a fungicidal or bactericitial' agent such as a solution of'8 -hy- One of the objects of the present invention is to provide a process whereby textiles; cordage',v paper. wood" and other cellulosic or part cellujlosic materials. may be impregnated with sum cient amount of relatively insoluble fungicidal agents in a singIe'ain'nnersi'on to: render the subsequently? dried cellulosie material p'ermar'iently and e'il'ectively'resistant' to. the action of fungus. and bacteria.

droxyquin'olin'e; ortho=phenyhphenoi-or"chloro- A further; object is to provide a novel fungus phenyl phenol; and subsequently dried, the fab ric will attain some-"degree of resistance to fungi cidal and bactericidal action; However; subse-- quent wetting or" laundering of the fabric thus t'ericidal agent andLthereby' to 'reducedrastically" the-resistanceof=- the fabric to fungi and bacteria; In order to fix the fungicidal -agent on the ric; it has been proposed to' form the metallic salt of the agentwitiiin'the interstices- 0f the fab- 'ric': Sincethe metallic's'a'lts'ofmany of'the fungi cidal agents such as 8-hydroxyquinoline-=and"the chlorophenols are rel'atively' insolublein most media: for treating'fabrics: it has been proposed toempl'oy a"'method"whereby' after immersion in e a solution of a fungicidal agent of'this type; the fabrici's drained' andsubsequently'passedthrough? a solution of'a water-solublemetal saltsuch as calcium; magnesiumorpther alkaline earth acetates; zinc; aluminum; copper; cadmium, mer- 80 oury' or other heavy metal" acetates" or nitrates whereby the metal" salt of tliefungioidal agent is precipitated on thefabrie: This-'method offikingthe fungicidalagent" on the fabric" has certain disadvantages. For example; afabric treated by' the-two-bathmethod hereinbef-ore described anti subsequently dried contains soluble salts which leach out when the" cloth is subsequently" laun de-reii-orsubjeetewtwweathering conditions; im"'- pairingthe residual protectiom against fungus "9 and bacteria. Moreover; the two-batik methodrequires additional equipment and an increased' cost for-the applicati'oir or the treatment:

In addition; many' of tlie=- best-known fungicidal agents'embodying'heavy metal saltsof sub'stances and bacteria-proofing composition.

Other objects will become apparent from the following description and examples.

The improved fungicide-proofing, composition. of the present invention comprises a water-in.- oil emulsioneontaining. in the oilphase thereof a rfelativeli water insolubl'e fungicidal agent, suchas copper 8'-hyd'roxyquinoline,. amodified alkydl' resin havinga relatively high ratio of fatty a'cid residue to, phthalic" anhydride residu'e,.-and a mix.- t'ure'of chlorinated. dis'phenyls.- As a further embodimentoffthe invention, a part orall of'the. modified alkyd resin may be present in the composition" inthe formof. an ammonium soap.

Suitable fungicidal" agents for the purpose of thepresent 'i'nvention are copper 8-hydroxyquinoline; copper" SQV -di-bromo-8 hydroxyquinoline,. copper 5,'7'-dichloro-8-hydroxyquinoline, 551-111- brominated' hydroxyquinoline, 5,7 -dichloro-8-hy.- droxyquinol'ine and: copper pentachlorophenate. Other metallicsalts may. be employed in place oi v the copper salts, for example, zinc,-- cadmiumaluminum or. calcium salts.v The copper salts are much, to be preferred however, since they are by far the mosteflective: from the: standpoint of in-- solubilityand permanency when incorporated in the. cel-lulesic. material.

Modified-. alkyd== resins: Suitab1er f01 the purpose of vthe' -present invention arerth'osewhich arerpre pared i'romiatty oilssand; fatty acids; suchas linseedoil: and: linseed oil: fatty" acids;v phthalic anhydrideianduglycerol; Other fatty: oils or acids: or: mixtures'thereof; such as; a-zmixt-ure of linseed. oiL. dehydrated? castor: oil a'n'di linseed: oil fatty" swirls;vaw. mixture of linseed: oil an dehydratedcaster: 0117.. or as. mixture: or: linseed oil, soya bean oirand soya team fatty acids; may b'e eniployd' inithe preparation of the" resin; Likewise; other polyhydroxw' alcohols, such as" pentaerythritol; may-betemployed in'iplacei or 'glifcerol; Maleic' or 3 fumaric acids may be employed in place of part or all of the phthalic anhydride. It is understood that these substitutions give rise in alterations to the properties of the resins. However, as explained hereinbefore, those resins which are soluble in mineral spirits and which emulsify mineral spirits are the resins contemplated as components of the composition of the present invention. Likewise, ammonium soaps formed by the addition of ammonia to the modified alkyd resins which fall in this category are also contemplated as components of the composition of the present invention. Suitable modified alkyd resins for the purpose of the present invention are those which contain for example, from -40% by weight of v I phthalic anhydride residue and which are soluble in mineral spirits and serve as emulsifying agents for mineral spirits.

The chlorinated diphenyls suitable as components of the composition of this invention are the mixtures of chlorinated diphenyls obtained by chlorinating diphenyl and which mixtures contain from 20-68% of chlorine. Also included are those chlorinated diphenyls which contain in ad dition various proportions of chlorinated ter phenyls. Some of these mixtures are liquid at room temperature and others may be melted, for example, on heated metal rolls to become liquids at temperatures ranging from 30-140 C.

The composition of the present invention may also contain a flame-retarding agent such as am timony pentoxide in amounts ranging from 24.0% of the weight of the composition, in which event the quantity of the chlorinated diphenyls may be increased to an amount in the range of 10-25% of the weight of the composition.

The emulsion composition of the present inven' tion may contain any desired proportions of water phase to oil phase in the range of 1:4 to 4:1. A desirable proportion is that of 50 parts of Water and 50 parts of oil. The quantity of modified a1- kyd resin employed in the composition may be varied over a wide range, for example, from 2% or less to 10% or more. based on the emulsion composition. The quantity of ammonia employed to form a soap with the residual acidic constituents of the modified alkyd resins depends on the extent to which soap formation isdesired and may range from part to total consumption of the acidity available in the resin for this purpose. The quantity of chlorinated diphenyl mixture which may be employed in the composition may be varied over a wide range, for example, from 3% or less to or more. The quantity of fungicidal agent, such as copper S-hydroxyquinoline, may be varied over a wide range, depending upon the particular fungicidal agent selected, the amount of the agent which is absorbed from the composition in the treatment of a particular of application, the composition be brushed on the fabric. paper or wood article. Like ,e. the drying operation may be accomplished in any desired manner, for example. by exposing the respective surfaces of the treated article multaneously or successively to air streams which may he at room temperature or higher ternperatures below the charring point of the ce1- lulosic materials. Textiles, coriiage, paper and Wood treated with the composi ent invention are found to be i to the action of fungus and bacteria. IJIOIQOVQI'. the resistance is characterized by a high degree of permanency even when the treated cellulosic material is subjected to severe weathering, or in the application to textiles and carriage, to suc cessive launderings.

The fungicidal and bactericidal composition of the present invention may be formed in any type of cellulosic substance to be treated and the A amount of the fungicidal agent which is desired on the cellulosic substance after the treatment. Desirable quantities of fungicidal agent in general of the composition of the present invention may range from or less to 5% or more.

In employing the fungus-proofing composition of the present invention, cellulosic materials, such as textiles, cordage, paper or wood, are immersed in the composition to impregnate the cellulosic substance and then are dried. The impregnation may be accomplished in any desired manner, for example, by immersion in a vessel containing the composition, with or without the aid of squeeze rolls, either as a continuous operation or as a batch process. vFor some types I retention of the fungicidal agent within the i manner desired. A preferred method is that comprising blending the fungicidal agent, the modified alkyd resin and the chlorinated diphenyl on metal rolls, with the application of heat if necessary, until a smooth fluid paste formed. The paste is then dispersed. in mineral spirits. If the ammonium soap of the alkyd resin is to be formed. the necessary quantity of ammonia may be added to the blend on the rolls. or to the mineral spirits dispersion of the blend. Water is then added to the mixture and the mixture is agitated to form the emulsion, for example, by passing the mixture through a colloid mill. While the permanency of many of the fungicidal agents of the type hereinheforc described is substantially enhanced by ap lication to the cellulosic material by means of the com-- position of the present invention, very out-stand ing results in this respect are obtained when the fungicidal agent in the composition is SJY-di bromo-8-hydroxyquinoline, copper 5,7 -dihromo- 8-hydroxyquinoline, 5,7 dichloro 8 hydroxy-- quinoline, copper dichloro-8-hydrcxyquinoline or copper 8-hydroxyquinoline. These substances in particular are representative of the various fungicidal and bactericidal agents of the type contemplated in the composition of the present invention.

While the alkyd resin in the composition of the present invention aids in the placement and terstices of the cellulosic material, also irn parts to the treated cellulosic material .a certain degree of water repellency. However, it is sirable to treat the cellulosic substance further with a water repellent in order to attain a hi h degree of water repellency in the fabric treatewith the fungicidal composition. It is one the novel features of the present invention that the composition of the present invention is compatible with a wide variety of water-proofing emulsion compositions and water-proofing cornponents. These water-proofing compositions and components may be acidic, neutral or alkaline in character. Moreover, the application to cellulosic materials of the composition of the present invention containing a wateraepellent emulsion has been found to enhance the gree of permanency of resistance of the ce1lulosic material to the action of molds and par ticularly when the treated cellulosic materials are subjected to soil burial tests.

Typical water-repellent compositions which may be incorporated in the composition of the present invention are those which comprise aqueous suspensions of waxes and soaps, thermo-setthe resulting compositions according to the method of the present example were found to possess excellent water repellency. Moreover, the treated specimens were found to contain substantially 1% of the fungicidal agent, and protection against the attack by molds was found to be substantially permanent.

Example IV The following composition was prepared:

Pounds Copper pentachlorophenate 2.5 Modified alkyd resin 3.0 Chlorinated diphenyl mixture (62% chlorine) 5.0 Ammonium hydroxide (28%) 1.5 Mineral spirits 43.0 Water 45.0

The components, with the exception of the mineral spirits and water, were blended together by the method of Example I. The blend was added to the mineral spirits and dispersed therein. Subsequently the water was added, and the mixture was passed through a colloid mill. Cotton duck fabrics, section of lumber for ammunition boxes, cordage and paper were treated with the composition of this example by immersion in a vessel containing the composition, excess material was drained from the specimen, and the specimen was allowed to air dry. The specimens upon analysis were found to contain sufficient of the fungicidal agent to protect the specimen against the action of molds. Moreover, the degree of permanency of the protection was found to be very satisfactory. In place of copper pentachlorophenate, any other substantially waterinsoluble salt of pentachlorophenol may be employed, for example, the calcium, barium, lead, zinc, aluminum, mercury or cadmium salts of pentachlorophenol. These pentachlorophenates are distinguished from the halogenated 8-hydroxyquinoline derivatives and copper salts thereof, and also copper B-hydroxyquinoline in that the pentachlorophenates appear to produce fungicidal action by the hydrolysis of the salts in the presence of moisture, whereas the halogenated 8-hydroxyquinoline derivatives and the copper salts thereof appear to produce fungicidal action by mere contact of the agent with the mold organisms. It is of interest also that the copper salts of the halogenated and unhalogenated 8- hydroxyquinoline appear from experimental observations to be the only metal salts of these substances which inhibit mold growth completely when applied in the composition of the present invention.

Portions of specimens of cellulosic substances, including wood, paper, textiles and cordage treated with the compositions described in Examples I to IV were exposed to the action of various molds. The treated textile specimens were tested against the organisms ChaetOnium globosum, Aspergillis niger, Penicillium sp., Metarrhizium sp. by the method described in the Corps of Engineers, U. S. Army, Tentative Specification No. T1452A, entitled Processing Fabrics, Coordage and Threads for Mildew-Proofing, dated J anuary 15, 1943, paragraphs F3a (3) to 3a (8), inclusive. growth on the treated specimens. Untreated specimens exposed under similar conditions were heavily attacked by the various species of fungus. Other portions of the textile and cordage specimen were laundered for 40 minutes in soap water There was no evidence of fungus phase comprising /2-5% at 100 C., rinsed free of soap, dried and exposed to the same molds. There Was no evidence of fungus growth on the laundered and exposed specimens. Other portions of the textile and Cordage specimens were leached in running water for 200 hours, dried and exposed to the molds. Additional specimens were buried in moist soil rich in acidic humus for a period of several weeks. Upon inspection, the exposed, treated specimens were found to be substantially free of fungus growth.

I claim:

1. A fungus-proofing composition for the treatment of cellulosic substances comprising a waterin-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion having an oil phase comprising -5% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of 8--hydroxyquinoline and of pentachlorophenol, 2-10% of an oil-modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 31-25% of a chlorinated diphenyl mixture containing from 20-68% of chlorine, and mineral spirits.

2. A fungus-proofing and W8.t8l--13l'00fil'lg composition for the treatment of cellulosic substances comprising 1) a water-in-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion-having an oil of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of 8-hydroxyc1uinoline and of pentachlorophenol, 210% of an oilmoclifiecl alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits,

". 13-25% of a chlorinated diphenyl mixture containing from 20-68% of chlorine and mineral spirits and (2) admixed therewith a water-repellent emulsion containing as the water repellent component thereof, a substance selected from the group consisting of water repellent waxes, soaps and resins.

3. A fungus-proofing and water-proofing ccmposition for the treatment of cellulosic substances comprising (1) a water-in-oil emulsion in which 1 the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion having an oil phase comprisin -5% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of 8-hydroxyquino- .1 line and of pentachlorophenol, 2-1G% of an oi modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing 20-68% of chlorine and mineral spirits and (2) a water-repellent agent selected from the group consisting of water repellent waxes, soaps, and resins.

4. A fungus-proofing and water-proofing composition for the treatment of cellulosic substances comprising (1) a water-in-oil emulsion in which the ratio of water phase to oil phase is in the ec aa phase comprising a imc at range of 1:4 to"4":l, said emulsion'having an oil /25% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of B-hydroxyquiholine and of pentachlorophenol,2-l0% of an oilmodified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifyingsubstance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing 20-68% chlorine, and mineral spirits and (2) a tetramethylol melamine resin admixed therewith.

5. A fungus-proofing and water-proofin composition for the treatment of cellulosic substances comprising (1) a water-in-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion having an oil phase comprising /25% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of S-hydroxyquinoline and of pentachlorophenol, 2-10% of an oil-modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 325% of a chlorinated diphenyl mixture containing from 20-68% chlorine, and mineral spirits, and (2) a hydrocarbon wax in combination with an N-acylated alkylene polyamide.

6. A fungus-proofing and water-proofing composition for the treatment of cellulosic substances comprising (1) a water-in-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4: 1, said emulsion having an oil phase comprising /;5% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of 8-hydroxyquinoline and of pentachlorophenol, 2-10% of an oil-modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing from 20-68% chlorine, and mineral spirits and (2) a tetramethylol melamine resin in combination with an N-acylated alkylene polyamide.

7. A fungus-proofing and water-proofing composition for the treatment of cellulosic substances comprising (1) a water-in-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion having an oil phase comprising /2-5% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of B-hydroxyquinoline and of pentachlorophenol, 2-10% of an oilmodified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing from 20-68% chlorine, and mineral spirits and (2) a tetramethylol melamine resin in combination with a hydrocarbon wax and an N-acylated alkylene polyamide.

8. As an articleof manufacture, a textile containing within its interstices a composition, comprising a watch-insoluble fungicidal agent, an oilmodified alkyd resin and a chlorinated diphenyl mixture, Jsaid article being prepared by imp nating a textile with -'a water-in-oil emulsion having an oil phase comprising /2-'5% of a waterinsoluble fungicidal agentsselected from the group consisting of water-insoluble salts of 8-;hydroxyquinoline and of pentachlorophenol, 2-10% of an oil-modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifyin substanceselected-from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said 'resinbeing soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing 20-68% chlorine, and mineral spirits, said treated textile being subsequently dried.

9. As an article of manufacture, a textile containing within its interstices a composition comprising a water-insoluble fungicidal agent, an oilmodified alkyd resin, a chlorinated diphenyl mixture and a water-repellent agent selected from the group consisting of water repellent waxes, soaps, and resins, said article being prepared by impregnating a textile with a Water-in-oil emulsion having in its oil phase /2-5% of a water-insoluble fungicidal agent selected from the group consisting of water-insoluble salts of S-hydroxyquinoline and of pentachlorophenol, 2-10% of an oil-modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phhtalic anhydride, said resin being soluble in mineral spirits, 3-25% of a chlorinated diphenyl mixture containing 20-68% chlorine and mineral spirits, said emulsion containing admixed therewith a water-repellent agent selected from the group consisting of water repellent waxes, soaps, and resins and said textile being subsequently dried and heated at a temperature in the range of -1'70 C.

10. A process of treating textiles, wood, cordage and paper articles to render them fungusproof comprising applying the composition described in claim 1 to said articles, and subjecting the treated articles to a drying operation.

11. A process for rendering textiles, wood, cordage and paper articles fungus-proof and waterproof comprising applying the composition described in claim 2 to said articles, subjecting said treated articles to a drying operation and subsequently heating said articles at a temperature in the range of 120-170 C.

12. A fungus-proofing composition for the treatment of cellulosic substances comprising a water-in-oil emulsion in which the ratio of water phase to oil phase is in the range of 1:4 to 4:1, said emulsion having an oil phase comprising /2-5% of copper B-hydroxyquinoline, 2-10% of an oil modified alkyd resin made from a polyhydroxy alcohol, phthalic anhydride and a modifying substance selected from the group consisting of fatty oils and fatty acids, said resin containing 20-40% of phthalic radical calculated as phthalic anhydride, said resin being soluble in mineral spirits, 3-25% of chlorinated diphenylmixture containing from 20-60% of chlorine, and mineral spirits.

13. A fungus-proofing and water-proofing composition for the treatment of cellulosic substances comprising (1) a water-in-oll em si n in w ich soluble in mineral spirits, 325% of a chlorinated 1 diphenyl mixture containing from 20-68% ch10- rine and mineral spirits, and (2) a water repellent agent selected from the group consisting of water repellent waxes, soaps and resins admixed therewith.

PAUL GEORGE BENIGNUS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,066,363 Patterson Jan. 5, 1937 2,127,526 OKane Aug. 23, 1938 2,282,181 Guinzburg Ma 5, 1942 2,386,492 Sobel Oct. 9, 1945 

